Process for producing electrically conductive composites and composites produced therein

ABSTRACT

Production of electrically conductive composites comprising a dielectric porous substance, e.g., fiberglass fabric, and a pyrrole polymer in the pores of such substance, by treating the porous substance with a liquid pyrrole, and then treating the resulting porous substance with a solution of a strong oxidant in the presence of a non-nucleophilic anion, such as ferric chloride. The pyrrole monomer is oxidized to a pyrrole polymer, which precipitates in the interstices of the porous material. Alternatively, the dielectric porous material can first be treated with a solution of strong oxidant and non-nucleophilic anion followed by treatment with liquid pyrrole, to precipitate an electrically conductive polypyrrole in the pores of the material. The resulting composite of porous material, e.g., fiberglass fabric, containing polypyrrole is electrically conductive while the other properties of such impregnated conductive porous material are substantially unaffected. Several treatments of the porous substance with the pyrrole and oxidant solutions can be carried out to increase the electrical conductivity of the composite.

BACKGROUND OF THE INVENTION

The present invention relates to the production of electricallyconductive composites, and is particularly concerned with a process forconferring varying degrees of conductivity on electrically nonconductiveporous structural materials, and the resulting electrically conductivecomposites.

In the past several years organic polymers have been discovered whichhave metallic properties, particularly electrical conductivity up toabout 1000 ohm⁻¹ cm⁻¹. These polymers include doped polyacetylene andpolypyrrole.

Although there are many potential applications for conducting polymers,their use has been limited by the fact that they are chemicallyunstable, have poor mechanical properties and/or are difficult toproduce in suitable forms.

Polypyrrole which is chemically more stable, for example, than the dopedpolyacetylene, has the disadvantage of being very brittle. Thinfree-standing polypyrrole films from about 10 μm to 20 mil thick havebeen produced on electrodes by electrochemical polymerization. However,these prior art films are too thin and too brittle to be useful in moststructurally related applications. Particularly, the brittleness of suchconducting polymer films renders their handling for large areaapplications extremely difficult, if not impossible.

Polypyrrole is produced by electropolymerization as described by A. F.Diaz, et al., in an article entitled "Electrochemical Polymerization ofPyrrole" in the Journal of Chemical Society, Chemical Communications,1979, page 635. N-substituted analogs of pyrrole such asN-methyl-pyrrole and N-phenylpyrrole have been used to form polymers asreported by A. F. Diaz, et al., in an article entitled."Electrochemistry of Conducting Polypyrrole Films" in the Journal ofElectroanalytical Chemistry, 129, (1981) pages 115-132. The productsproduced in these processes are thin (from 20 μm to 30 μm) freestandingfilms in which anions from the electrolyte, such as tetrafluoborate andperchlorate, are used to dope the polymer and balance the cationiccharge of the polymer backbone. However, the resultant polymer film isbrittle and does not have the bulk and ductility needed to make thematerial useful in structural-related applications.

U.S. Pat. No. 4,401,545 to Naarmann, et al., discloses electricallyconductive polypyrrole complexes with nitroaromatic anions as dopants,prepared by the anodic oxidation of a pyrrole in a polar solvent, in thepresence of a salt of an acidic nitroaromatic compound. However, thethickness of the resulting electrochemically produced polypyrrolecomplexes is limited and the resulting films are also relatively brittleand hence also have limited structural applicability.

U.S. Pat. No. 4,394,304 to Wnek, discloses a method of forming aconductive polymer by impregnating a processable polymer such aspolyethylene or polystyrene, with a Ziegler Natta catalyst, exposing theimpregnated polymer to acetylene gas to form polyacetylene within amatrix of the initial polymer, and introducing a dopant, such as iodine,into the polyacetylene, to form a conductive polymer blend. However, amajor disadvantage of the resulting conductive polymer blend is the factthat it is unstable when exposed to air or to water.

U.S. application Ser. No. 646,716, filed Sept. 4, 1984, now U.S. Pat.No. 4,582,575, patented Apr. 15, 1986, titled "Electrically ConductiveComposites and Method of Preparation," of L. F. Warren, Jr., L. Maus andD. S. Klivans, and assigned to the same assignee as the presentapplication, discloses electrically conductive composites comprising adielectric porous substance, e.g., fiberglass fabric, and a pyrrolepolymer deposited in the pores of such substance. The composites areproduced by contacting the porous substance with an anode in anelectrolytic cell containing an electrolyte comprising a pyrrole monomerand a substantially non-nucleophilic anion such as bisulfate, andpassing an electric current through the cell, thus electrochemicallyprecipitating a conductive pyrrole polymer in the pores of suchsubstance.

An object of the present invention is to readily confer varying degreesof conductivity on porous structural materials.

Another object of the invention is to provide a procedure for obtainingan electrically conductive composite formed of a substantiallynon-conductive or dielectric porous substance and a conductivepolypyrrole, which is stable and has good mechanical properties.

A still further object of the invention is the provision of a processfor depositing a polypyrrole within a dielectric porous structuralmaterial to produce an electrically conductive composite.

SUMMARY OF THE INVENTION

The above objects are achieved according to the invention and astructural material rendered electrically conductive, by contacting astructural material which is porous, e.g., a fiberglass fabric, with aliquid pyrrole or a solution of the pyrrole, and then contacting thematerial with a solution of a strong oxidant, such as ferric ion, in thepresence of a substantially non-nucleophilic anion, such as chlorideion, e.g., as provided by ferric chloride. The pyrrole is thus oxidizedand polypyrrole is chemically precipitated in the pores or intersticesof the material, and the resulting impregnated composite renderedelectrically conductive.

Alternatively, the porous structural material can be contacted ortreated first with a solution of a strong oxidant, and the so-treatedmaterial can then be contacted with a liquid pyrrole or a solution ofpyrrole, in the presence of a non-nucleophilic anion, to oxidize thepyrrole and precipitate polypyrrole within the interstices of thematerial, to form an electrically conductive composite.

Several (two or more) treatments of the substrate, e.g., fiberglassfabric, with the pyrrole and oxidant solutions can be carried out toincrease the conductivity of the final composite.

The degree of conductivity conferred upon the porous structural materialby the precipitation of the conductive pyrrole polymer into the pores ofthe material can vary, the magnitude of conductivity depending upon thevolume of the pores occupied by the pyrrole polymer, and other factorssuch as the ratio of pyrrole to substituted pyrrole, where a mixture ofpyrrole monomers is employed in the pyrrole treating solution, theconcentration of the pyrrole and oxidant solutions and the number oftreatments of the substrate with such solutions. Thus, a porousdielectric or electrically insulating structural material such asfiberglass can be rendered conductive to varying degrees according tothe present invention.

These and other objects and features of the invention will becomeapparent from the following detailed description thereof.

DETAILED DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS

According to one embodiment of the invention, a structural material,which is a dielectric or electrically insulating material, and which isporous to the extent that it possesses voids or interstices which canhold small amounts of liquid, is dipped into the liquid pyrrole orpyrrole solution, or a mixture of pyrrole and a substituted derivativethereof, such as an N-substituted pyrrole, the material removed, andexcess liquid is drained away. The wet material or substrate is thendipped into a solution containing a strong oxidant and including anon-nucleophilic anion, such as Fe³⁺ and Cl⁻, respectively, derived fromferric chloride, resulting in the oxidation of the pyrrole and thechemical deposition of a polypyrrole, or a copolymer of pyrrole and asubstituted derivative thereof, which to a major extent remains withinthe interstices of the material.

In another embodiment, the porous dielectric material is treated withthe liquid pyrrole or pyrrole solution by applying such liquid pyrroleor solution to the material, followed by treatment of the wettedmaterial with an oxidant solution, by applying the oxidant solution tothe material.

The electrically conductive polymer thus deposited in the pores of thestructural material or substrate comprises a cationic polypyrroleportion and an antionic portion derived from the non-nucleophilic anion,e.g., chloride. After air-drying, the dielectric material impregnatedwith the conductive pyrrole polymer is electrically conductive.

In carrying out the invention process, porous dielectrics orelectrically insulating structural materials can be used, such as aporous ceramic, a porous glass, e.g., a frit, a porous or reticulatedorganic foam, e.g., polyurethane, a fabric, which can be woven ornon-woven, e.g., fiberglass fabric, a mixed oxide fabric such as analumina/silica/boria fabric, e.g., Nextel, or a synthetic organic fabricsuch as Kevlar, a trademark of the DuPont Company, for aromaticpolyamide fiber, a polyester such as Dacron cloth, and the like. Theinsulating material can vary in thickness but should have pores whichare sufficiently large to retain liquid. An insulating substrate such asfiberglass fabric, can have a thickness ranging from about 1 to about 20mils, usually about 2 to about 10 mils.

The liquid pyrrole treating solution can comprise neat liquid pyrrole, aC-substituted pyrrole, such as a 3- or 3,4- alkyl or aryl substitutedpyrrole, e.g., 3-methylpyrrole, 3,4-dimethylpyrrole, 3-phenylpyrrole or3-methyl-4-phenylpyrrole, an N-substituted pyrrole, e.g., anN-alkylpyrrole, such as N-methylpyrrole, or an N-arylpyrrole such asN-phenylpyrrole, or a substituted N-phenylpyrrole such asnitrophenylpyrrole, to obtain the corresponding conductive pyrrolehomopolymer. For production of a conductive copolymer, a mixture ofpyrrole and a C- or an N-substituted derivative of pyrrole, as describedabove, can be employed. The use of substituted pyrroles results in lowerconductivity polymers than the parent polypyrrole. Hence the use ofpyrrole is preferred for higher conductivity applications.

The pyrrole solution may or may not contain a solvent. The solvents usedcan be any organic solvent in which pyrrole and the oxidant are soluble,and which does not interfere with the desired oxidation reaction. Suchsolvents include alcohols, ethers, e.g., dioxane, acetone, acetonitrile,tetrahydrofuran, methylene chloride, and the like. Water, alone or incombination with a water miscible solvent also can be employed. Theconcentration of the pyrrole in the solvent can vary but generally is inthe range from about 0.03 to about 2 molar.

The oxidation of pyrrole or a substituted derivative thereof to producethe conductive pyrrole polymer is carried out in the presence of astrong oxidant. The term "strong oxidant" as employed herein is intendedto denote any oxidizing substance which is capable of oxidizing pyrroleor a substituted derivative thereof as defined above, to producepolypyrrole or a pyrrole copolymer.

Examples of strong oxidants include the cations Fe³⁺, Cu²⁺, Ce⁴⁺, NO⁺and (C₆ H₅)₃ C⁺. Examples of compounds providing the above cations asoxidizing agents are the soluble salts of the above cations such asferric perchlorate, ferric chloride, cupric fluoborate, cupricperchlorate, nitrosyl hexafluorophosphate triphenylmethyl fluoborate,ceric sulfate and the like.

Other suitable oxidizing agents such as an anion, e,g., the persulfateanion, can be employed.

Further, instead of employing oxidents in the form of cations or anions,neutral oxidants such as hydrogen peroxide in an acid solution, e.g., indilute sulfuric acid, can be employed.

A material providing substantially non-nucleophilic anions functioningas dopant for the pyrrole polymer is also employed, preferably inconjunction with the oxidant. These anions are generally strong acidanions such as sulfate, bisulfate, perchlorate, fluoborate, PF₆ ⁻, AsF₆⁻ and SbF₆ ⁻ anions. Chloride anion also can be used, even though it issomewhat nucleophilic.

Examples of compounds providing such anions are the free acids and thesoluble salts of such acids, e.g., the alkali metal salts. Examples ofsuch compounds include sulfuric acid, sodium sulfate, sodium bisulfate,sodium perchlorate, ammonium fluoborate, hydrogen hexafluoroarsenate,and the like. In addition, the nonnucleophilic anion can be a sulfonatesalt or sulfonic acid anion derived from an organic sulfonate or anorganic sulfonic acid, e.g., as provided by p-toluenesulfonate andpolymeric sulfonates, e.g., polystyrenesulfonate and polyvinylsulfonate,and trifuoromethylsulfonate, CF₃ SO₃ ⁻. Also organic sulfate anion suchas dodecylsulfate can be employed.

Although the oxidant as cation and the non-nucleophilic anion can beprovided by separate compounds, a convenient manner for providing boththe strong oxidant and non-nucleophilic anion is in the form of a saltincorporating both the oxidant cation and the non-nucleophilic anion, asexemplified by the above-noted compounds ferric perchlorate, ferricchloride, cupric fluoborate, cupric perchlorate, and the nitrosyl andtriphenylmethyl salts. When ferric chloride is used, thenon-nucleophilic anions present include FeCl₄ ⁻ and FeCl₄ ²⁻, as well aschloride ion.

Where, for example, ammonium persulfate is used as the oxidant of thepyrrole dissolved in dilute sulfuric acid, the persulfate anion is theoxidizing agent and the non-nucleophilic anion is the HSO₄ ⁻ orbisulfate anion derived from the sulfuric acid. If hydrogen peroxide isemployed as oxidant in a sulfuric acid medium, the non-nucleophilicanion again is the bisulfate anion.

The oxidant which preferably also incorporates the non-nucleophilicanion, e.g., as in ferric chloride, can be dissolved in water to form anaqueous solution, or such oxidant can be dissolved in an organicsolvent, dependent on its ability to dissolve the particular oxidantsalt and its inertness with respect to such oxidant salt such that theoxidant retains its ability to oxidize the pyrrole in the presence ofthe solvent. Where separate compounds providing the oxidant andnon-nucleophilic anion are provided, such solvent should be capable ofsuitably dissolving both compounds.

Examples of suitable solvents include alcohols, acetone, acetonitrile,tetrahydrofuran and methylene chloride. Thus, for example, theabove-noted ferric salts can be dissolved in acetone, acetonitrile,tetrahydrofuran or methylene chloride. The triphenylmethyl salts arebest employed in methylene chloride. The ferric or ceric salts can alsobe employed in aqueous solution.

The same or different solvents can be employed in the pyrrole and theoxidant solutions.

Although in preferred practice the non-nucleophilic anion or anionproducing material is present in the oxidant solution, if desired, suchanion or anion producing material can be provided in a solution separatefrom the oxidant solution. Further, if desired, the non-nucleophilicanion can be incorporated in the pyrrole solution.

The concentration of oxidant material or cation in aqueous or solventsolution can range from about 0.001 to about 2 molar, preferably about0.1 molar, and the concentration of non-nucleophilic anion or anionproducing material also can range from about 0.001 to about 2 molar,preferably about 0.1 molar.

The treatment of the porous dielectric material in the liquid pyrroleand in the oxidant solution is generally carried out in both instancesat ambient or room temperature. However, the temperature can be higheror lower. Also, in preferred practice such treatments are carried out inthe presence of oxygen in the air.

The time of treatment of the porous substrate in the pyrrole and oxidantsolutions is long enough to penetrate the interstices of the porousmaterial with the liquid pyrrole or pyrrole solution and to obtainsufficient penetration of the oxidant solution therein, or vice versa,to permit the precipitation reaction to occur in the interstices orpores. The oxidation reaction is frequently relatively slow, and canrequire several minutes, e.g., about 1 to 5 minutes for completion,during which time the substrate darkens as the polymerization reactionproceeds.

The polypyrrole which is thus chemically precipitated remains within theinterstices of the dielectric porous material after drying thereof. Suchdrying of the polypyrrole impregnated porous material following removalthereof from the oxidant solution and rinsing with the same solvent asemployed therein, can be carried out in the air at ambient or elevatedtemperature up to about 100° C.

Treating the porous substrate such as fiberglass fabric with thepyrrole. e.g., neat liquid pyrrole or a solution of pyrrole, by wettingor applying such liquid or solution to the porous substrate by means ofa liquid dispenser, as by spraying or brushing, followed by similarlyapplying an oxidant solution to the wetted fabric, results in a better,more adherent deposit of the pyrrole polymer than the dipping orimmersion procedure, since the latter procedure often results in polymerprecipitation off the substrate into the solution.

If desired, the porous substrate can be treated first with the oxidantsolution, followed by treatment of the substrate containing the oxidantsolution in the interstices thereof, with the liquid pyrrole or pyrrolesolution.

The dried porous material impregnated with pyrrole polymer has anelectrical conductivity which can be measured with a standard 2-probeohmmeter apparatus, and such conductivity generally corresponds to asheet resistivity ranging from about 100,000 to about 50 ohms/square.The term "ohms/square" as a measure of sheet resistivity is defined asthe bulk resistivity of the sample which is expressed in ohms×cm dividedby the thickness in cm. Sheet resistivity is proportional to thereciprocal of electrical conductivity. The other properties of theimpregnated conductive porous material or substrate are substantiallyunaffected by the impregnated conductive polymer. Thus, the resultingcomposite substantially retains the same mechanical properties that itpossessed prior to impregnation.

To increase the conductivity of the porous material impregnated withpyrrole polymer, additional or repeated treatments of, for example, afabric with a pyrrole and oxidant solution often are required to buildup the polymer level in the material. Hence, the conductivity of thepolymer impregnated substrate can be adjusted by the number of suchtreatments, as well as by varying the concentrations of the pyrrole andoxidant solutions.

The following are examples of the invention, it being understood thatsuch examples are only illustrative and in no sense limitative of theinvention.

EXAMPLE I

A piece of 7781 fiberglass fabric marketed by Uniglass Industries, LosAngeles, Calif., was first treated with enough neat liquid pyrrole bymeans of an applicator to penetrate the fabric.

The wetted fiberglass fabric was then treated with a 0.1 molar solutionof anhydrous ferric chloride in acetone, by means of an applicator.Conductive polypyrrole formed of polypyrrole doped with chloride andalso with chloroiron anions such as FeCl₄ ⁻ and FeCl₄ ²⁻, wasprecipitated in the interstices of the fabric. The resulting compositewas then allowed to develop at ambient temperature for 5 minutes, washedwith acetone and allowed to dry.

The resulting electrically conductive composite had a sheet resistivityof 15,000 ohms/square, as measured by a two-probe ohmmeter, relative toessentially infinite sheet resistivity for the initially untreated 7781fiberglass fabric.

EXAMPLE II

The procedure of Example I was substantially followed except that thefiberglass fabric was first treated with the ferric chloride in acetonesolution, and the fiberglass fabric containing ferric chloride in theinterstices thereof, was then treated with neat pyrrole, to precipitatepolypyrrole in the interstices of the fabric.

The polypyrrole impregnated fiberglass fabric or substrate had a sheetresistivity approximately the same as the sheet resistivity of thepolypyrrole impregnated fiberglass fabric obtained in Example I.

EXAMPLE III

The procedure of Example I was substantially followed, except that thefiberglass fabric was first dipped into liquid pyrrole, the fiberglassfabric containing pyrrole in the interstices thereof was removed fromthe liquid pyrrole, excess liquid was drained from the material, and theresulting wetted material was then dipped into the ferric chloride inacetone solution.

The resulting electrically conductive composite had a sheet resistivitysomewhat less than that of the composite of Example I.

EXAMPLE IV

The procedure of Example I was essentially followed except that in placeof liquid pyrrole, a mixture of 70 mole % pyrrole and 30 mole %N-methylpyrrole was employed.

In this example, a conductive copolymer of pyrrole and N-methylpyrrolewas formed in the interstices of the fiberglass fabric, comprised of thepyrrole copolymer cation and chloride and chloriron anions. Theresulting fiberglass fabric impregnated with the pyrrole copolymer had asheet resistivity of about 30,000 ohms/square.

EXAMPLE V

The procedure of Example I was essentially followed except employing asthe oxidant a solution of 0.5 molar cupric perchlorate in acetonitrile.

The resulting dried composite of the fiberglass substrate impregnatedwith polypyrrole doped with perchlorate had a sheet resistivity of about1500 ohms/square.

EXAMPLE VI

The procedure of Example I was substantially followed except that ferricperchlorate (0.1 molar) in acetonitrile was employed instead of theferric chloride-acetone solution.

An electrically conductive composite of the fiberglass impregnated withpolypyrrole doped with perchlorate was obtained. Such composite had asheet resistivity of 30,000 ohms/square. A second treatment of the samecomposite in liquid pyrrole followed by treatment in the ferricperchlorate solution resulted in a lower sheet resistivity of 2,000ohms/square.

EXAMPLE VII

The procedure of Example I was substantially followed but employing asolution of 0.2 molar ammonium persulfate in dilute (2%) sulfuric acid,instead of the ferric chloride-acetone solution.

An electrically conductive composite of the fiberglass fabricimpregnated with polypyrrole doped with bisulfate was obtained, thecomposite having a sheet resistivity of 1500 ohms/square.

The electrically conductive composites of the invention have varioususes including the production of electrodes, batteries, switches,semi-conductor components, and in anti-static applications, e.g.,anti-static finishes for plastics, electromagnetic interferenceshielding applications and as electrical conductors.

From the foregoing, it is seen that the invention provides a novelprocedure for chemical deposition of a conducting pyrrole polymer withina porous dielectric material or substrate so as to confer varyingdegrees of electrical conductivity upon the porous structural material.

Since various changes and modifications of the invention will occur toand can be made readily by those skilled in the art without departingfrom the invention concept, the invention is not to be taken as limitedexcept by the scope of the appended claims.

What is claimed is:
 1. A process for producing an electricallyconductive composite which comprises the steps of:(a) contacting adielectric porous substance with a liquid pyrrole, (b) contacting saidporous substance with a solution of a strong oxidant capable ofoxidizing pyrrole to a pyrrole polymer, .Iadd.said strong oxidant beinga cation selected from the group consisting of Ce⁴⁺, NO⁺ and (C₆ H₅)₃ C⁺cations, .Iaddend.and (c) oxidizing said pyrrole by said strong oxidantin the presence of a substantially non-nucleophilic anion, andprecipitating a conductive pyrrole polymer in the pores of saidsubstance.Iadd., said non-nucleophilic anion being selected from thegroup consisting of sulfate, bisulfate, fluoroborate, PF₆ ⁻, AsF₆ ⁻, andSbF₆ ⁻ anions.Iaddend..
 2. The process of claim 1, wherein step (a) iscarried out prior to step (b).
 3. The process of claim 1, wherein step(b) is carried out prior to step (a).
 4. The process of claim 1, saidcontacting steps (a) and (b) being carried out by applying said liquidpyrrole and said oxidant solution to said porous substance or byimmersion of said porous substance in said liquid pyrrole and saidoxidant solution.
 5. The process of claim 1, including carrying out aplurality of treatments of said porous substance with said liquidpyrrole and said oxidant solution.
 6. The process of claim 1, saidpyrrole monomer selected from the group consisting of pyrrole, a 3- and3,4-alkyl and aryl C-substituted pyrrole, an N-alkylpyrrole and anN-arylpyrrole. .[.7. The process of claim 1, said strong oxidant being acation selected from the group consisting of Fe³⁺, Cu²⁺, Ce⁴⁺, NO⁺ and(C₆ H₅)₃ C⁺ cations..].
 8. The process of claim 1, said strong oxidantbeing an anion.
 9. The process of claim 8, said oxidant anion being thepersulfate anion. .[.10. The process of claim 1, said non-nucleophilicanion being selected from the group consisting of sulfate, bisulfate,perchlorate, chloride, fluoborate, PF₆ ⁻, AsF₆ ⁻, and SbF₆ ⁻ anions..].11. .[.The process of claim 1,.]. .Iadd.A process for producing anelectrically conductive composite which comprises the steps of:(a)contacting a dielectric porous substance with a liquid pyrrole, (a)contacting said porous substance with a solution of a strong oxidantcapable of oxidizing pyrrole to a pyrrole polymer, said strong oxidantbeing a cation selected from the group consisting of Fe³⁺, Cu²⁺, Ce⁴⁺,NO⁺ and (C₆ H₅)₃ C+ cations, and (c) oxidizing said pyrrole by saidstrong oxidant in the presence of a substantially non-nucleophilicanion, and precipitating a conductive pyrrole polymer in the pores ofsaid substance, .Iaddend.said non-nucleophilic anion being selected fromthe group consisting of p-toluenesulfonate, polystyrenesulfonate,polyvinylsulfonate, the corresponding free sulfonic acids, anddodecylsulfate.
 12. The process of claim 11, said non-nucleophilic anionbeing derived from the free acids or the soluble salts of said acids..[.13. The process of claim 1, said oxidant and said non-nucleophilicanion being provided by a compound selected from the group consisting offerric perchlorate, ferric chloride, cupric fluoborate and cupricperchlorate..].
 14. The process of claim 1, said oxidant and saidnon-nucleophilic anion being provided by a compound selected from thegroup consisting of triphenylmethyl fluoborate and nitrosylhexafluorophosphate.
 15. The process of claim 1, said pyrrole beingpresent in aqueous or organic solvent medium in which said pyrrole andsaid oxidant are soluble and which does not interfere with the oxidationreaction.
 16. The process of claim 1, including an organic solvent forsaid oxidant, said solvent being inert with respect to said oxidant andpermitting said oxidant to oxidize said pyrrole.
 17. The process ofclaim 1, said oxidant and said non-nucleophilic anion being present inaqueous solution.
 18. The process of claim 1, said pyrrole being presentin a concentration in the range from about 0.03 to about 2 molar, saidoxidant being present in the range of about 0.001 to about 2 molar, andsaid non-nucleophilic anion being present in a concentration in therange from about 0.001 to about 2 molar.
 19. The process of claim 1,said dielectric porous substance selected from the group consisting of aporous ceramic, porous glass, a porous organic foam, and a fabric. 20.The process of claim 19, said porous substance being a fabric selectedfrom the group consisting of fiberglass fabric, mixed oxide fabric and asynthetic organic fabric.
 21. The process of claim 20, said poroussubstance being fiberglass fabric.
 22. A process for producing anelectrically conductive composite which comprisescontacting .[.the.]..Iadd.a .Iaddend.dielectric porous substance with a liquid pyrrole,contacting the resulting substance containing liquid pyrrole in thepores thereof with a solution of a strong oxidant capable of oxidizingpyrrole to a pyrrole polymer and a substantially non-nucleophilic anion,.Iadd.said strong oxidant being a cation selected from the groupconsisting of Fe³⁺, Cu²⁺, Ce⁴⁺, NO⁺ and (C₆ H₅)₃ C⁺ cations,.Iaddend.and oxidizing said pyrrole by said strong oxidant andprecipitating a conductive pyrrole polymer comprising a pyrrole polymercation and a substantially non-nucleophilic anion in the pores of saidsubstance.Iadd., said non-nucleophilic anion being selected from thegroup consisting of p-toluenesulfonate, polystyrenesulfonate,polyvinylsulfonate, the corresponding free sulfonic acids, anddodecylsulfate.Iaddend.. .[.23. A process for producing an electricallyconductive composite which comprises contacting the dielectric poroussubstance with a solution of a strong oxidant capable of oxidizingpyrrole to a pyrrole polymer, and a substantially non-nucleophilicanion, contacting the resulting substance containing said solution ofstrong oxidant and substantially non-nucleophilic anion in the poresthereof, with a liquid pyrrole, and oxidizing said pyrrole by saidstrong oxidant and precipitating a conductive pyrrole polymer in thepores of said substance, and pyrrole polymer comprising a pyrrolepolymer cation and a substantially non-nucleophilic anion..]. .[.24. Theprocess of claim 22, said pyrrole monomer selected from the groupconsisting of pyrrole, a 3- and 3,4-alkyl and aryl C-substitutedpyrrole, an N-alkylpyrrole and an N-arylpyrrole, said strong oxidantbeing a cation selected from the group consisting of Fe³⁺, Cu²⁺, Ce⁴⁺,NO⁺ and (C₆ H₅)₃ C⁺ cations, and said non-nucleophilic anion beingselected from the group consisting of sulfate, bisulfate, perchlorate,chloride, fluoborate, PF₆ ⁻, AsF₆ ⁻, and SbF₆ ⁻ anions..]. .[.25. Theprocess of claim 24, said oxidant and said non-nucleophilic anion beingprovided by a compound selected from the group consisting of ferricperchlorate, ferric chloride, cupric fluoborate and cupricperchlorate..].
 26. The process of claim .[.24,.]. .Iadd.22,.Iaddend.employing pyrrole, said pyrrole being present in aconcentration in the range from about 0.03 to about 2 molar, saidoxidant being present in the range of about 0.001 to about 2 molar, andsaid non-nucleophilic anion being present in a concentration in therange from about 0.001 to about 2 molar.
 27. The process of claim 26,said porous substance being a fabric selected from the group consistingof fiberglass fabric, mixed oxide fabric and a synthetic organic fabric..[.28. The process of claim 23, said pyrrole monomer selected from thegroup consisting of pyrrole, a 3- and 3,4-alkyl and aryl C-substitutedpyrrole, an N-alkypyrrole and an N-arylpyrrole, said strong oxidantbeing a cation selected from the group consisting of Fe³⁺, Cu²⁺, Ce⁴⁺,NO⁺ and (C₆ H₅)₃ C⁺ cations, and said non-nucleophilic anion beingselected from the group consisting of sulfate, bisulfate, perchlorate,chloride, fluoborate, PF₆ ⁻, AsF₆ ⁻, and SbF₆ ⁻ anions..]. .[.29. Theprocess of claim 28, said pyrrole being present in a concentration inthe range from about 0.03 to about 2 molar, said oxidant being presentin the range of about 0.001 to about 2 molar, and said non-nucleophilicanion being present in a concentration in the range from about 0.001 toabout 2 molar..]. .[.30. The process of claim 29, said porous substancebeing a fabric selected from the group consisting of fiberglass fabric,mixed oxide fabric and a synthetic organic fabric..].
 31. Anelectrically conductive composite produced by the process of claim 1..[.32. An electrically conductive composite produced by the process ofclaim 7..].
 3. An electrically conductive composite produced by theprocess of claim .[.10.]. .Iadd.11.Iaddend..
 34. An electricallyconductive composite produced by the process of claim
 18. 35. Anelectrically conductive composite produced by the process of claim 20.36. An electrically conductive composite produced by the process ofclaim
 22. .[.37. An electrically conductive composite produced by theprocess of claim 23..]. .Iadd.38. A process for producing anelectrically conductive structural composite which comprises the stepsof:(a) contacting a dielectric porous structural substance with a liquidpyrrole, (b) contacting said porous substance with a solution of astrong oxidant capable of oxidizing pyrrole to a pyrrole polymer, saidstrong oxidant being a cation selected from the group consisting ofFe³⁺, Cu²⁺, Ce⁴⁺, NO⁺ and (C₆ H₅)₃ C⁺ cations, and (c) oxidizing saidpyrrole by said strong oxidant in the presence of a substantiallynon-nucleophilic anion, and precipitating a conductive pyrrole polymerin the pores of said substance, said non-nucleophilic anion beingselected from the group consisting of p-toluenesulfonate,polystyrenesulfonate, polyvinylsulfonate, the corresponding freesulfonic acids, and dodecylsulfate. .Iaddend..Iadd.39. The process ofclaim 38, said pyrrole being present in aqueous medium in which saidpyrrole and said oxidant are soluble and which does not interfere withthe oxidation reaction. .Iaddend..Iadd.40. The process of claim 38, saiddielectric porous substance selected from the group consisting of aporous glass, a porous organic foam, and a fabric. .Iaddend..Iadd.41.The process of claim 38, said porous substance being a fabric selectedfrom the group consisting of fiberglass fabric, mixed oxide fabric and asynthetic organic fabric. .Iaddend..Iadd.42. The process of claim 38,said porous substance being fiberglass fabric. .Iaddend..Iadd.43. Theprocess of claim 38, said oxidant and said non-nucleophilic anion beingpresent in aqueous solution. .Iaddend..Iadd.44. An electricallyconductive composite produced by the process of claim 38..Iaddend..Iadd.45. An electrically conductive composite produced by theprocess of claim
 44. .Iaddend.